48
J. Zhang et al. / Journal of Fluorine Chemistry 116 (2002) 45±48
1
(10 mmHg). A hydroscopic white solid (4c, 7.1 g, 11.1 mmol,
97%) was sublimed out. (CF3 SO2N(H)SO2CF2 CF2 )2O 4c
2F, m), À120.1 (e or f, 2F, m), À121.7 (e or f, 2F, m); H
a
b
c
NMR d 11.1 (s).
(dry CD3CN) 19F NMR d À76.6 (a, 6F, s), À80.0 (c, 4F, m),
1
À113.2 (b, 4F, m); H NMR d 11.5 (s).
3.6. Fluorination of ethyl 4-nitrobenzoyl acetate using
5a and 5c
3.4. Preparation of CF3SO2NFSO2RFSO2NFSO2CF3,
RF (CF2)4 5a, (CF2)2O(CF2)2 5c
Into a CH2Cl2 (10 ml) solution of ethyl 4-nitrobenzoyla-
cetate (0.3 mmol) was added 5 mg of anhydrous Na2CO3
and 0.15 mmol 5a at 22 8C and the reaction mixture was
stirred for 5 h. The reaction mixture was diluted with ethanol
(5 ml) and water (20 ml), extracted by CH2Cl2 (2 Â 10 ml),
rinsed with brine and dried over Na2SO4. Pure ethyl
2-¯uoro-3-(40-nitrophenyl)-3-oxo-propanate (91%) was
obtained by column chromatography on silica gel using
hexane/ethyl acetate (3/1) as the eluent. Reaction with 5c
was carried out in the same way (90% yield). 19F NMR d
À190.8 (d, 2JHF 48 Hz); 1H NMR d 1.3 (3H, t), 4.7 (2H,
In a typical reaction, 4a (1.0 g, 1.6 mmol) was placed into
an 80 ml stainless steel bomb reactor and evacuated. Fluor-
ine (6.0 mmol) was condensed into the reactor at À196 8C
and the reactor was allowed to slowly warm to 22 8C, and
then kept in a 50±60 8C water bath for 14 days. After
pumping out excess unreacted F2 through a soda-lime
column, a colorless solid (0.9 g, 1.4 mmol, 88%) was recov-
ered from the bomb. (CF3 SO2N(F)bSO2CF2 CF2 )2 5a
(m.p. 28±29 8C) 19F NMR d À32.0 (b, 2F, br, s), À71.9
(a, 6F, s), À105.9 (c, 4F, m), À119.4 (d, 4F, m); IR (KCl,
cmÀ1) 1462 (s), 1222 (vs), 1145±1126 (s), 1031 (w), 856 (s),
a
c
d
2
q), 6.0 (1H, d, JHF 48 Hz), 8.27, 8.38 (4H, AB-type).
a
c
d
769 (w), 726 (w), 637 (w). (CF3 SO2N(Fb)SO2CF2 CF2 )2O
5c (colorless liquid) 19F NMR d À32.2 (b, 2F, br, s), À72.0
(a, 6F, m), À80.6 (d, 4F, m), À110.0 (c, 4F, m); IR (KCl,
cmÀ1) 1464 (s), 1344 (s), 1219 (vs), 1146 (s), 1075 (w), 993
(w), 96 (w), 852 (m), 771 (w), 646 (w).
Acknowledgements
The authors are grateful to the National Science Founda-
tion for ®nancial support of this research.
3.5. Preparation of CF3SO2NFSO2RFSO2NFSO2CF3,
RF (CF2)6 5b
References
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5b, 20% for 5b0) was obtained. The NMR was obtained on
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